Carrying out catalytic reactions



May 23,*1939. M PIER ET Au (.'ARRYING OUT CATALYTIC REACTIONS Filed Jan. )9, 1935 2v Sheets`Sheet 1 i T/ u @T KSQ.. SSXQB 8 n rob @mm w G E 5w A mmml, m E u v2.80 3585 MSSS l May 23, 1939. y M. PIER ET AL CARRYING OUT CATALYTIC REACTIONS Filed"A Jan. 9, 1935 Pre/eater Coder 2 Sheets-Sheet '2 Benzelne Mai/lans Peler Wader Szmon Pew/J -Jacob INVENToRs TH E l R ATTORNEYS Patented May z3, 1939 UNITED STATES 8.150.511 l CARRYING OUT CATALYTIC REACTIONS lathias Pier, Heidelberg, and Walter Simon and MIMI,

llymesne en-on-the-lthine, Geramignments, to

naar. admon. Standard-I. G; Company, N. J., a corperatio'nofDelaware amm .mm1-y a, 193s, serai No. 1,022

'In Germany January 11, 1984 'IClahlla 'Ihe present invention relates to improvements in carrying out catalytic reactions, in particular the destructive hydrogenation of` distillable i carbona'ceous materials.

It has already been proposedin our Patent No, 2,039,259 dated April 28, 1936 to carry out catalytic reactions with canbustible carbonaoeous materials, in fparticular destructive hydrogenations, in the presence of catalysts which have been prepared by. decomposition of sulpho salts oi' heavy metals atan elevated temperature.

We have now found that it is advantageous to employ metal sulphides which have been obtained by a conversion of thio salts with compounds of metals different from those containing as metall lic constituents yonly alkali-metals and alkaline earth metals, in particular with heavy metal compounds, while dispersed-in an inert ordinarilyliquid medium, for example in aqueous solution or suspension or in the presence lori.' organic solvents. By theterm inert" as applied in delining-the liquid medium,it is understood that the liquid medium does not enter into any reaction with the compound or the salt dispersed in it other than possibly to effect the dissociation of any such compound or salt that does dissolve in it. However, it istolbe imderstood that while the liquid medium in some speciilc cases may cause dissociation or ionization, it is not necessary inl all cases that dissociation or ionization-occur in order for the reactions embraced in this invention to properlytake place. The said compounds, of course, may contain an alkali metal or alkaline earth metal, as forexample alums or sodiumzinc sulphate though heavy metal compounds containing no alkali metals or alkaline earth metals lare preferable. The term thio salts is employed herein to mean the salts of oxygen acids of metallic elements the oxygenv oi' which um or germanium. 'I'hese are brought together oxides, hydroxides or salts of these metals, as

for example the halides, sulphates, nitrates, oxides, hydroxides, carbonates'of copper, silver,

zinc, manganese, aluminium, titanium, tin, lead,

(ci. iss-ss) vanadium, chromium, molybdenum, tungsten,

uranium, magnesium, iron, `nickel and cobalt, which maybe employed in the dispersed state, for example in the form of their aqueous solutions or v suspensions or dissolved or suspended in organic solvents,- 'I'he metal compounds preferably contain a metal diiierent from those contained in the thio salt employed. It is oi special advantage to carry out the said conversion in the presence' o! organic solvents, such as' acid amides, for example yformamide, acid chlorides, for example acetyl chloride, amino acids, keto acids, esters, nltriles, amines, aldehydes, alcohols, ketones and nitro compounds. It is preferable to provide for the exclusion of water when employing the said solvents.

For the preparation of the catalysts, for example. -the thiosalts and also the metal compounds are wholly or partly dissolved at ordinary or elevated temperature in one or two of the said solvents. Both solutions or suspensions are then brought together at ordinary or elevated temperature and at atmospheric or increased pressure, if desired while stirring and/or leading in a volatile compound of bivalent sulphur, especially hydrogen sulphide or carbon disulphide. A

sulphide is thus precipitated which contains two or more metals.

gether two solutions oi' which one contains diss' For example bybringing tosolved ammonium thiotungstate in cyclohexylamine and the other dissolved cobalt chloride in acetone, a sulphide is precipitated consisting of cobalt tungsten sulphide. If by the action of hydrogen sulphide or carbon disulphide the metal compound is converted into the corresponding sulphide in such a manner that no conversion with the thio compound would take place, hydrogen sulphide or carbon disulphide are not employed. Solutions or suspensions of the reactants may also be combined in which more than one metal compound and/or thio salt are wholly or partly dissolved or suspended.

The sulphides formed may be dried and aftertreated'with gases such as hydrogen, volatile sulphur compounds or the like, at elevated temperature and at atmospheric or increased pressure, for example in the manner described in our beforementioned Patent No. 2,039,259.

`The precipitation of the sulphide may also be carried out in the presence of a carrier, as for example active carbon, active silica, active alumina, bentonite, Florida earth, bauxite, pumice, magnesite,-magnesia and chromium oxide. 'Ihe sulphides may also be applied to the carriers after precipitation. The catalysts may also be employed in admixture with other catalytic substances, as for example diiilcultly reducible metal oxides, such as zinc oxide, titanium oxide or ahnnina.

"I'he said catalysts arelvery suitable for the production of valuable hydrocarbons by the re-` divided state and preferably in small amounts.

. tion of 1 molecular proportion of ammonium thio 'I'he catalysts are also suitable for the cracking of liquid carbonaceous materials or for the dehydrogenation of hydrocarbons or their derivatives.

other catalytic reactions, such as the purlnl cation of gases, the-preparation of methanol or hydrocarbons from carbon monoxide and hydrogen, the preparation of hydrogen sulphide from its elements, the preparation of hydrogen or of polymerization products from the waste gases from destructive hydrogenations or from cracking gases, and like reactions, may also be carried out with the aid of the said catalysts.

Our invention is further illustrated by the accompanying drawings and examples butl our invention is not to be considered as restricted thereto. In the drawings:

Fig. 1 is a diagrammatic illustrationof a suitable apparatus for preparing our.catalyst; and

Fig. 2 is a diagrammatic illustration of a suit- .able apparatus for carrying out our process of destructive hydrogenation.

Eaample 1 A freshly' prepared solution of 0.54 molecular proportion of titanium tetrachloride in benzine may be prepared as indicated in Figure 1 by adding the titanium tetrachloride and the benzine to al vessel I provided with a suitable stirrer Il. This, solution is then gradually added to a solutungstate in cyclohexylamine. This latter may be obtained by supplying ammonium thio tungstate and cyclohexylamine toa vessel I2 equipped with stirrers I3. The solutions from the vessels I0 and I2 are Apassed `through lines I5 and It controlled by valves I1 and I8 respectively to a vessel I 9 equipped with a stirrer 2| and provided with a cooling Jacket 2l through which cooling water may be circulated. The brown precipitate thus formed isfiltered oil' by a suctionfilter 25 and is freed from adherent solvent by extraction with organic solvents of low boiling point, such for example as acetone or alcohol, which vmay be supplied from a tank 20 to asprinkler 21 which is adapted to feed the solvent to the 'suction' filter. After this treatment, the precipitate is passed through a steam drying chamber .III and to an oven 3i, having a mechanical feed I2 therein.' Hydrogen and hydrogen sulphide are supplied to this oven at a temperature of from 300 C. to 400 C. The'conveyor means molds the grey-black mass thus obtained or the mass may be molded by pressure in' an hydraulic press 'or inv a tablet-making' machine.

This mass constitutes. the catalyst which is placed in a tube 40, 'as shown in Figure 2, which.

is heated at about 410 C. in a current of hydrogen under a pressure of 200 atmospheres. 'I'he vapors of the gas oil (boiling between 200 C. and 350 C.) obtained by cracking from German crude oil are fed from a tank 4I and a pump 42 Ato a heat exchanger 43. Hydrogen is compressed by a compressor-44 and is fed by a pump 45 to the heat exchanger l4I where it is mixed with the gasoil vapors. From the heat exchanger the gas oil vapors.and hydrogen are passed to the preheater or furnace 4I by which they are raised 'to the temperature of.410 C. above mentioned and are passedI through the catalyst in the tube 40. The treated vapors are withdrawn through a line A4", passed through the heat exchanger 43, then through a cooler 48 andseparator 49 to Iseparate the benzine which may be removed by a line 50, the vapors being returned by a line 5I to the pump 45. The product thus obtained may consist of 70% of benzine which may be directly employed as motor fuel without further refining and of 30% of illuminating oil.

Example 2 An aqueous solution of 1 molecular proportion of cobalt chloride is united with a 5 per cent aqueous solution of 1 molecular proportion of ammonium thiotilngstate which has been freshly prepared in the cold state. The precipitated black compound is filtered off by suction, washed with water, dried in an atmosphere of lnitrogen and then aftertreated at from 350 to 360 C.- in a current of dry hydrogen.

loA

' lThe catalyst, moulded by means of a press, is

rigidly arranged' in a high-pressure chamber, and a middle oil, prepared by the destructive hydrogenation of mid-German brown coal, is lea thereover in the form of vapor together with Vhydrogen under a pressure of 250 atmospheres at 430 C. A product is obtained which consists to the extentof 60 per cent of benzine free from phenol. The remaining 40 per cent is led again over the catalyst together with fresh middle oil and thus converted into benzine.

Example 3 To a cold aqueous solution of one molecular proportion of ammonium thio molybdate is .added a solution of two thirds of molecular proportions of ferrous sulphate. The iron-molybdenum sulphide thereby precipitated is dried while excluding air, treated with hydrogen at 300 C., pressed to pills and then rigidly arranged in a high pressure vessel. If the vapors of the middle oil 'fraction boiling between 200 and 375 C. of Va mineral oil are passed togetherwith hydrogen at a temperature of 415 C. and under a pressure of 200 atmospheres over the thus prepared catalyst a product'is obtained of which 60 per cent consists of valuable benzine and of which the remainder-represents an excellent illuminating oil.

. Y Example 4 An alcoholic solution of anhydrous nickel chloride is added to a freshlyprepared solution` of ammonium thio vanadate in 'cyclohexylamine The resulting precipitate is freed from cyclo` hexylamine and ammonium-chloride formed by the conversion by extraction with alcohol and then dried while excluding air. The dried sub-- stance vis subjected to an aftertreatment at 300 C. with hydrogen containing` 25 per cent of hydrogen sulphide and is thereupon pressed to pieces and rigidly arranged in a highpressure vessel. If the vapors of the benzine obtained by cracking a mineral oil rich in sulphur are passed together with khydrogen at 370 C. and

under a pressure of 180 atmospheres over the thus prepared catalyst a product is obtained which is free from gum forming substances and which contains only 0.005 per cent of sulphur.

Example 5 An alcoholic suspension of freshly prepared ammonium thio stannate is stirred for about 8 hours together with an alcoholic solution of anhydrous iron chloride present in the same molecular proportion as the ammonium thiostannate. The resulting iron-tin sulphide is added in an amount oi' 0.1 per cent to a nely ground Uerman gas tlame coal which has been made up into a paste with a heavy oil from the destructive hydrogenation of the same coal; thereupon the paste lis heated in a coil together with hydrogen and under a pressure of 300 atmospheres to a temperature of 460 C. and subsequently passed through a high pressure reaction vessel which is maintained at the same temperature. In this manner 96 per cent of the coal are converted mainly into liquid products.

What we claim is:

1. 'I'he process which comprises treating combustiblek carbonaceous materials heavier than gasoline under conditions to efiect destructive hydrogenation at a temperature between 300 C. and 700 C., under superatmospheric pressure and in the presence of a metal sulphide catalyst lso which has been prepared by dispersing a thio salt in an inert ordinarily liquid medium, said thio salt being of the form oi' a salt of an oxygen bustible 'carbonaceous materials heavier thanl gasoline under conditions to effect destructive ,hydrogenation, at a temperature between 300 C.

Aand 700 C., under superatmospheric pressure and in the presence of a metal sulphide catalyst which has been prepared by dispersing a thio salt containing ammonium as cation in an inert ordinarily liquid medium, said thio salt being of the form of a salt of an oxygen acid of a metallic element the'ioxygen of which has beentreplacedby sulphur, dispersing in an inert ordinarily liquid medium such a compound of a heavy metal substantially i'ree from alkali metals and alkaline earth metals as is capable of entering into reaction with said thio salt with the formation of a metal sulphide, and combining the dispersion of the said thio salt with the dispersion of said metal compound\so that reaction therebetween takes place.

3. The process which -comprises treating combustible carbonaceous materials heavier than gasoline under conditions to effect destructive hydrogenation, at va temperature between 300 C. and 700. C., under superatmospheric pressure and in the presence of a metal sulphide catalyst which has been prepared by dispersing a thio salt containing ammonium as cation in water, said thio salt being of the form of a salt of an oxygen acid of a metallic element the oxygen of which has been replaced by sulphur, dispersing in water such a compound of a heavy metal as is capable' of entering into reactionwith said thio salt with the formation of a metal sulphide, and combining the dispersion of the said thio salt with. the dispersion of said metal compound so that reaction therebetween takes place.

4. The process which comprises treating combustible carbonaceous materials heavier than gasoline under conditions to eect destructive hydrogenation, at a temperature between 300 C. and 700 C., Vunder superatmospheric pressure and inthe presence of a metal sulphide catalyst which has been prepared by dispersing a thio salt containing ammonium as cation in an organic solvent, said thio salt being of the form of a salt of an oxygen acid of a metallic element the oxygen of which has been replaced by sulphur, dispersing in an organic solvent such a compound of a heavy metal as is capable of entering into reaction .with said thio salt with the formation oi a metal sulphide, and combining the dispersion of the said thio salt with the dispersion of said metal compound so that reaction therebetween takes place.

5. The process which comprises treating combustible carbonaceous materials heavier than gasoline under conditions to effect destructive hydrogenation and in the presence of a metal sulphide catalyst which has been prepared by dispersing a thio salt in an inert ordinarily liquid medium, said thio salt being ofthe form of a salt of an oxygen acid of va metallic element the oxygen of which has been replaced by sulphur, dispersing in an inert ordinarily liquid medium such a compound of a metal different from those containing as metallic constituents only alkali metals and alkali earth metals as is capable of entering into reaction with said thio salt with' the formation of a metal sulphide, and combining the dispersion of the said thio salt with the dispersion oi said metal compound so that reaction therebetween takes place.

6. 'I'he process which comprises treating combustible carbonaceous materials heavier than gasoline under conditions to eilect destructive hydrogenation and in the presence of a metal sulphide catalyst which has been prepared by dispersing a thio salt containing ammonium as cation in water, said thio salt being of the form of a salt of an oxygen acid of a metallic element the oxygen of which has been replaced by sul\`l phur, dispersing in water such a compomid of a heavy metal substantially free from alkali metals and alkaline earth metals as is capable of entering'into reaction withy said thio salt with the formation of a metal sulphide, and combining the dispersion of the said thio salt with the dispersion of'said metal compound so that reaction therebetween takes place.

7. vThe process which comprises treating combustible carbonaceous materials heavier than gasoline under conditions to eil'ect destructive hydrogenation and in the presence of a metal sulphide catalyst which has been prepared by dispersing a thio salt containing ammonium as cation in an organic solvent, said thio salt being of the form of a salt of an oxygen acid of a metallic element the oxygen of which has been replaced by sulphur, dispersing in an organic solvent such a compound of a heavy metal-substantially free from alkali metals and alkaline earth metals as is capable of entering into reaction with said thio salt, with the formation oi' a metal sulphide, and combining the dispersion of the said thio salt with the dispersion oi' said metal compound so that reaction therebetween takes place.

MATHIAS PIER. WALTER SIMON. PAUL JACOB. 

